CN103450144A - Method for preparing epsilon-caprolactone through biomimetic catalysis of cyclohexanone oxidation - Google Patents
Method for preparing epsilon-caprolactone through biomimetic catalysis of cyclohexanone oxidation Download PDFInfo
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- CN103450144A CN103450144A CN2013104153355A CN201310415335A CN103450144A CN 103450144 A CN103450144 A CN 103450144A CN 2013104153355 A CN2013104153355 A CN 2013104153355A CN 201310415335 A CN201310415335 A CN 201310415335A CN 103450144 A CN103450144 A CN 103450144A
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- general formula
- caprolactone
- pimelinketone
- hydrogen
- metalloporphyrin
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- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 238000000034 method Methods 0.000 title claims abstract description 38
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 15
- 230000003647 oxidation Effects 0.000 title abstract description 7
- 238000007254 oxidation reaction Methods 0.000 title abstract description 7
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 title abstract 3
- 230000003592 biomimetic effect Effects 0.000 title abstract 2
- 239000001301 oxygen Substances 0.000 claims abstract description 21
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 229910052751 metal Inorganic materials 0.000 claims abstract description 17
- 239000002184 metal Substances 0.000 claims abstract description 17
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract 3
- JBFHTYHTHYHCDJ-UHFFFAOYSA-N gamma-caprolactone Chemical compound CCC1CCC(=O)O1 JBFHTYHTHYHCDJ-UHFFFAOYSA-N 0.000 claims description 29
- -1 phenyl aldehyde Chemical class 0.000 claims description 20
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 11
- 239000011664 nicotinic acid Substances 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- 239000012752 auxiliary agent Substances 0.000 claims description 8
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 8
- 229910052736 halogen Inorganic materials 0.000 claims description 8
- 150000002367 halogens Chemical group 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 8
- 229910052748 manganese Inorganic materials 0.000 claims description 8
- 230000001590 oxidative effect Effects 0.000 claims description 8
- GETTZEONDQJALK-UHFFFAOYSA-N (trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1 GETTZEONDQJALK-UHFFFAOYSA-N 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 6
- 229910052703 rhodium Inorganic materials 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 239000000460 chlorine Substances 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910052707 ruthenium Inorganic materials 0.000 claims description 4
- 150000002460 imidazoles Chemical class 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- 125000004429 atom Chemical group 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 150000003624 transition metals Chemical group 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 238000005516 engineering process Methods 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 239000007800 oxidant agent Substances 0.000 abstract 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 21
- 238000004817 gas chromatography Methods 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- 230000009466 transformation Effects 0.000 description 12
- 238000002360 preparation method Methods 0.000 description 3
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229920001610 polycaprolactone Polymers 0.000 description 2
- 239000004632 polycaprolactone Substances 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000006220 Baeyer-Villiger oxidation reaction Methods 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 150000004967 organic peroxy acids Chemical class 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 150000004032 porphyrins Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Landscapes
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Abstract
The invention discloses a method for preparing epsilon-caprolactone through biomimetic catalysis of cyclohexanone oxidation. In the method, cyclohexanone is used as a raw material, oxygen is used as an oxidizing agent, a metal phthalocyanine or metalloporphyrin compound is used as a catalyst, the reaction temperature is controlled at 25-120 DEG C, and the epsilon-caprolactone is obtained through a catalytic reaction under normal-pressure conditions. The method disclosed by the invention has the advantages of simple technology, mild conditions, high selectivity, safety, low cost and the like.
Description
Technical field
The present invention relates to a kind of preparation method of 6-caprolactone, specifically, relate to a kind of method that bionic catalysis oxidizing cyclohexanone prepares 6-caprolactone.
Background technology
6-caprolactone is a kind of important high molecular polymerization monomer, as the new polyester monomer, be widely used in polycaprolactone (PCL) and the blending and modifying resin of synthetic various different purposes, and as a kind of good organic solvent and important organic synthesis intermediate, some insoluble resins are shown to good solvability, can react with multiple compounds the fine chemicals that preparation has special performance.The method of industrial production 6-caprolactone mainly realizes by the Baeyer-Villiger oxidizing reaction at present, the oxygenant adopted is all that organic peracid is as Peracetic Acid usually, there are the problems such as poor stability, energy consumption be large in use procedure, make the application of this technique be restricted.
Adopt easy to use, be easy to get, safety and eco-friendly molecular oxygen/air prepare as oxygenant the trend that 6-caprolactone becomes research, wherein the bionic catalyst such as metalloporphyrin or metal phthalocyanine can activate oxygen under mild conditions, has safety, green, efficient, selectivity advantages of higher in catalytic oxidation.Chinese patent ZL 101205225A has reported that the oxidation of a kind of metalloporphyrin bionic catalysis ketone compounds prepares the method for lactone, the method relates to the process that pimelinketone B-V oxidation prepares 6-caprolactone, but have the problems such as auxiliary dosage large (be raw material 15 times), condition harshness, so the industrial application of the method is restricted.Patent ZL201110298626.1 has reported that the catalysis of metalloporphyrin pimelinketone dioxygen oxidation of simple structure prepares the method for 6-caprolactone, but in the method, used metal oxide or molecular sieve for promotor, had the shortcomings such as catalyst system complexity, separation difficulty.
Therefore, develop and a kind ofly take pimelinketone as raw material, oxygen is oxygenant, and mild condition, technique is simple, selectivity is high 6-caprolactone preparation technology will have very important application prospect.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, provide a kind of bionic catalysis oxidizing cyclohexanone to prepare the method for 6-caprolactone.
For realizing purpose of the present invention, the technical scheme adopted is: take pimelinketone as raw material, take oxygen as oxygenant, add organic solvent and auxiliary agent phenyl aldehyde, to there is the metal phthalocyanine of general formula (I) structure, the monokaryon metalloporphyrin of general formula (II) structure, the oxo metalloporphyrin of general formula (III) structure, μ-the oxygen of general formula (IV) structure-dinuclear metalloporphyrin is made catalyzer, being controlled at temperature of reaction is 25～120 ℃, carry out catalyzed reaction under the condition of normal pressure and obtain 6-caprolactone, wherein the concentration of catalyzer is 0.1-100ppm, the mol ratio of auxiliary agent phenyl aldehyde and raw material pimelinketone is 0.01～2,
M in general formula (I)
1be transition metal atoms Mg, Al, Cr, Mn, Fe, Co, Ni, Cu or Zn, R is hydrogen or carboxyl or sulfonic group; M in general formula (II)
2be atoms metal Cr, Mn, Fe, Co, Ni, Cu, Zn, Rh, Ru or Sn, X is halogen or hydrogen, R
1, R
2, R
3, R
4and R
5all be selected from hydrogen, halogen, nitro, alkyl, alkoxyl group, hydroxyl, carboxyl, sulfydryl or sulfonic group, dentate X
1chlorine or imidazoles or pyridine; M in general formula (III)
3atoms metal Mo, Fe, Mn, V, Ti, Ru or Rh, R
1, R
2, R
3, R
4and R
5all be selected from hydrogen, halogen, nitro, alkyl, alkoxyl group, hydroxyl, carboxyl, sulfydryl or sulfonic group; M in general formula (IV)
4atoms metal Al, Fe, Co, Mn, Zn, Ru or Rh, R
1, R
2, R
3, R
4and R
5all be selected from hydrogen, halogen, nitro, alkyl, alkoxyl group, hydroxyl, carboxyl, sulfydryl or sulfonic group.
In above-mentioned bionic catalysis oxidizing cyclohexanone prepares the method for 6-caprolactone, preferred catalyst levels is 1-50ppm, and preferred auxiliary agent phenyl aldehyde and raw material pimelinketone mol ratio are 0.5～2, and preferred temperature of reaction is 30-100 ℃.
In above-mentioned bionic catalysis oxidizing cyclohexanone prepares the method for 6-caprolactone, described solvent is one or more mixing in 1,2-ethylene dichloride, Isosorbide-5-Nitrae-dioxane, phenylfluoroform, n-butyl acetate, sec-butyl acetate, acetonitrile, ethyl acetate.
At first the present invention has synthesized metal phthalocyanine, metalloporphyrin class bionic catalyst, and catalyzer is solved homogeneously in solvent, and phenyl aldehyde is auxiliary agent, and under the condition existed at oxygen, the catalysis of pimelinketone oxidation generates 6-caprolactone.Bionic catalyst has activated molecular oxygen on the one hand, has also promoted on the other hand the initiation of free radical, after increasing by a series of free radical, forms the high price actives with strong oxidizing property energy, is easy to attack the carbonyl of pimelinketone, is conducive to the generation of 6-caprolactone.
Compared with prior art, the present invention has following beneficial effect:
1. to adopt oxygen be oxygenant in the present invention, avoided the safety issue of using peracid to bring.
2. the present invention has used with metal porphyrins or the metal phthalocyanine of biological enzyme similar structures and has made catalyzer, and the consumption of catalyzer and auxiliary agent is few.
3. low, the green safety of simple, the mild condition of operating procedure of the present invention, Financial cost, have good prospects for commercial application.
Embodiment
Below in conjunction with embodiment, the present invention will be further described, but protection scope of the present invention is not limited to the scope that embodiment means.
In embodiment, reagent used is commercially available analytical reagent.
In embodiment, the bionic catalyst such as metal phthalocyanine used, metalloporphyrin is by prior art (Alder AD, et al.J.Org.Chem.1967,32,476; Wang LZ et al.Org.Process Res.Dev.2006,10,757) described method is prepared.
Embodiment 1
Contain at 5mL the metal phthalocyanine (M that 50ppm has general formula (I)
1=Al, R=H), in sec-butyl acetate solution, add the pimelinketone of 1mmol and the phenyl aldehyde of 2mmol, passing into oxygen, is 70 ℃ of lower stirring reactions 6 hours in temperature, through the gas-chromatography inner mark method ration, detects and analyzes, the transformation efficiency of pimelinketone is 92%, and the yield of 6-caprolactone is 92%.
Embodiment 2
Contain at 5mL the metal phthalocyanine (M that 0.1ppm has general formula (I)
1=Mg, R=COOH), in phenylfluoroform solution, add the pimelinketone of 1mmol and the phenyl aldehyde of 1mmol, passing into oxygen, is 100 ℃ of lower stirring reactions 2 hours in temperature, through the gas-chromatography inner mark method ration, detects and analyzes, the transformation efficiency of pimelinketone is 80%, and the yield of 6-caprolactone is 80%.
Embodiment 3
Contain at 5mL the metal phthalocyanine (M that 10ppm has general formula (I)
1=Zn, R
1=COOH, R
2, R
3, R
4, R
5=H) in phenylfluoroform solution, add the pimelinketone of 1mmol and the phenyl aldehyde of 0.1mmol, pass into oxygen, in temperature, be 100 ℃ of lower stirring reactions 8 hours, detect and analyze through the gas-chromatography inner mark method ration, the transformation efficiency of pimelinketone is 83%, and the yield of 6-caprolactone is 83%.
Embodiment 4
Contain at 5mL the metalloporphyrin (M that 1ppm has general formula (II)
2=Cr, X=F, R
1, R
2, R
3, R
4, R
5=H, X
1for pyridine) 1, in the 2-dichloroethane solution, add the pimelinketone of 1mmol and the phenyl aldehyde of 0.5mmol, passing into oxygen, is 25 ℃ of lower stirring reactions 12 hours in temperature, through the gas-chromatography inner mark method ration, detects and analyzes, the transformation efficiency of pimelinketone is 89%, and the yield of 6-caprolactone is 88%.
Embodiment 5
Contain at 5mL the metalloporphyrin (M that 50ppm has general formula (II)
2=Rh, R
1, R
2, R
4, R
5=H, R
3=SO
3h, X
1for imidazoles) phenylfluoroform solution in, add the pimelinketone of 1mmol and the phenyl aldehyde of 1mmol, pass into oxygen, in temperature, be 120 ℃ of lower stirring reactions 2 hours, detect and analyze through the gas-chromatography inner mark method ration, the transformation efficiency of pimelinketone is 93%, and the yield of 6-caprolactone is 93%.
Embodiment 6
Contain at 5mL the metalloporphyrin (M that 100ppm has general formula (II)
2=Ru, R
1=C
2h
5, R
3=NO
2, R
2, R
4, R
5=H, X
1=Cl) in n-butyl acetate solution, add the pimelinketone of 2mmol and the phenyl aldehyde of 1mmol, pass into oxygen, in temperature, be 80 ℃ of lower stirring reactions 4 hours, detect and analyze through the gas-chromatography inner mark method ration, the transformation efficiency of pimelinketone is 95%, and the yield of 6-caprolactone is 95%.
Embodiment 7
Contain at 5mL the metalloporphyrin (M that 100ppm has general formula (III)
3=Mo, R
1, R
2, R
4, R
5=H, R
3=NO
2) acetonitrile solution in, add the pimelinketone of 1mmol and the phenyl aldehyde of 1.5mmol, pass into oxygen, in temperature, be 60 ℃ of lower stirring reactions 5 hours, through the gas-chromatography inner mark method ration, detect to analyze, the transformation efficiency of pimelinketone is 97%, the yield of 6-caprolactone is 97%.
Embodiment 8
Contain at 5mL the metalloporphyrin (M that 30ppm has general formula (III)
3=V, R
1, R
2, R
3, R
4, R
5=CH
3) ethyl acetate solution in, add the pimelinketone of 1mmol and the phenyl aldehyde of 2mmol, pass into oxygen, in temperature, be 30 ℃ of lower stirring reactions 6 hours, detect and analyze through the gas-chromatography inner mark method ration, the transformation efficiency of pimelinketone is 86%, and the yield of 6-caprolactone is 86%.
Embodiment 9
Contain at 5mL the metalloporphyrin (M that 10ppm has general formula (III)
3=Ru, R
1, R
2, R
3, R
4=H, R
5=COOH), in Isosorbide-5-Nitrae-dioxane solution, add the pimelinketone of 1mmol and the phenyl aldehyde of 1mmol, passing into oxygen, is 50 ℃ of lower stirring reactions 7 hours in temperature, through the gas-chromatography inner mark method ration, detects and analyzes, the transformation efficiency of pimelinketone is 93%, and the yield of 6-caprolactone is 93%.
Embodiment 10
Contain at 5mL the metalloporphyrin (M that 40ppm has general formula (IV)
4=Al, R
1, R
2, R
4, R
5=H, R
3=CH
3) 1, in the 2-dichloroethane solution, add the pimelinketone of 1mmol and the phenyl aldehyde of 1mmol, passing into oxygen, is 60 ℃ of lower stirring reactions 8 hours in temperature, through the gas-chromatography inner mark method ration, detects and analyzes, the transformation efficiency of pimelinketone is 90%, and the yield of 6-caprolactone is 90%.
Embodiment 11
Contain at 5mL the metalloporphyrin (M that 40ppm has general formula (IV)
4=Zn, R
1, R
3, R
4, R
5=H, R
2=SH) in n-butyl acetate solution, add the pimelinketone of 2mmol and the phenyl aldehyde of 1mmol, pass into oxygen, in temperature, be 100 ℃ of lower stirring reactions 5 hours, detect and analyze through the gas-chromatography inner mark method ration, the transformation efficiency of pimelinketone is 95%, and the yield of 6-caprolactone is 95%.
Embodiment 12
Contain at 5mL the metalloporphyrin (M that 60ppm has general formula (IV)
4=Ru, R
1=OCH
3, R
3=Cl, R
2, R
4, R
5=H) in phenylfluoroform solution, add the pimelinketone of 1mmol and the phenyl aldehyde of 1mmol, pass into oxygen, in temperature, be 90 ℃ of lower stirring reactions 6 hours, detect and analyze through the gas-chromatography inner mark method ration, the transformation efficiency of pimelinketone is 92%, and the yield of 6-caprolactone is 92%.
Claims (5)
1. a bionic catalysis oxidizing cyclohexanone prepares the method for 6-caprolactone, it is characterized in that take that pimelinketone is as raw material, take oxygen as oxygenant, add organic solvent and auxiliary agent phenyl aldehyde, to there is the metal phthalocyanine of general formula (I) structure, the monokaryon metalloporphyrin of general formula (II) structure, the oxo metalloporphyrin of general formula (III) structure, μ-the oxygen of general formula (IV) structure-dinuclear metalloporphyrin is made catalyzer, being controlled at temperature of reaction is 25～120 ℃, carry out catalyzed reaction under the condition of normal pressure and obtain 6-caprolactone, wherein the concentration of catalyzer is 0.1-100ppm, the mol ratio of auxiliary agent phenyl aldehyde and raw material pimelinketone is 0.01～2,
M in general formula (I)
1be transition metal atoms Mg, Al, Cr, Mn, Fe, Co, Ni, Cu or Zn, R is hydrogen or carboxyl or sulfonic group; M in general formula (II)
2be atoms metal Cr, Mn, Fe, Co, Ni, Cu, Zn, Rh, Ru or Sn, X is halogen or hydrogen, R
1, R
2, R
3, R
4and R
5all be selected from hydrogen, halogen, nitro, alkyl, alkoxyl group, hydroxyl, carboxyl, sulfydryl or sulfonic group, dentate X
1chlorine or imidazoles or pyridine; M in general formula (III)
3atoms metal Mo, Fe, Mn, V, Ti, Ru or Rh, R
1, R
2, R
3, R
4and R
5all be selected from hydrogen, halogen, nitro, alkyl, alkoxyl group, hydroxyl, carboxyl, sulfydryl or sulfonic group; M in general formula (IV)
4atoms metal Al, Fe, Co, Mn, Zn, Ru or Rh, R
1, R
2, R
3, R
4and R
5all be selected from hydrogen, halogen, nitro, alkyl, alkoxyl group, hydroxyl, carboxyl, sulfydryl or sulfonic group.
2. method according to claim 1, is characterized in that described catalyst levels is 1-50ppm.
3. method according to claim 1, the mol ratio that it is characterized in that auxiliary agent phenyl aldehyde and raw material pimelinketone is 0.5～2.
4. method according to claim 1, the temperature that it is characterized in that catalyzed reaction is 30-100 ℃.
5. method according to claim 1, is characterized in that described solvent is one or more mixing in 1,2-ethylene dichloride, Isosorbide-5-Nitrae-dioxane, phenylfluoroform, n-butyl acetate, sec-butyl acetate, acetonitrile, ethyl acetate.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103980078A (en) * | 2014-05-08 | 2014-08-13 | 中山大学 | Method for preparing lactone through catalyzing oxidation of ketone compound, and its special catalyst |
| CN104003971A (en) * | 2014-04-28 | 2014-08-27 | 上海应用技术学院 | Method for preparing epsilon-caprolactone through catalytic oxidation of cyclohexanone |
| CN105067740A (en) * | 2015-07-29 | 2015-11-18 | 中山大学惠州研究院 | Method for analyzing products generated during process of biomimetic catalytic cyclohexanone gas-liquid phase oxidation for producing epsilon-caprolactone |
| CN105130947A (en) * | 2015-07-21 | 2015-12-09 | 刘小秦 | Industrial production method of [epsilon]-caprolactone |
| CN111018823A (en) * | 2019-12-12 | 2020-04-17 | 河南能源化工集团研究总院有限公司 | Process for preparing epsilon-caprolactone and co-producing methacrylic acid by cyclohexanone |
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| CN102391238A (en) * | 2011-09-28 | 2012-03-28 | 江苏飞翔化工股份有限公司 | Method for preparing epsilon-caprolactone by catalyzing oxidation of cyclohexanone |
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| CN104003971A (en) * | 2014-04-28 | 2014-08-27 | 上海应用技术学院 | Method for preparing epsilon-caprolactone through catalytic oxidation of cyclohexanone |
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| CN105130947A (en) * | 2015-07-21 | 2015-12-09 | 刘小秦 | Industrial production method of [epsilon]-caprolactone |
| CN105130947B (en) * | 2015-07-21 | 2018-04-17 | 刘小秦 | A kind of industrial process of ε-caprolactone |
| CN105067740A (en) * | 2015-07-29 | 2015-11-18 | 中山大学惠州研究院 | Method for analyzing products generated during process of biomimetic catalytic cyclohexanone gas-liquid phase oxidation for producing epsilon-caprolactone |
| CN105067740B (en) * | 2015-07-29 | 2017-03-15 | 中山大学惠州研究院 | A kind of bionic catalysis cyclohexanone gas-liquid phase oxidation prepares the product analysis method of ε caprolactones |
| CN111018823A (en) * | 2019-12-12 | 2020-04-17 | 河南能源化工集团研究总院有限公司 | Process for preparing epsilon-caprolactone and co-producing methacrylic acid by cyclohexanone |
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